Kellogg process (steam reforming)

The starting mixture is natural gas.

The main component of natural gas is methane, it contains also significant traces of
other hydrocarbons, hydrogen sulphide and carbon dioxide.

CH4 + CO2 + H2S

1) Desulfurization:
H2S (g) +ZnO (s) ZnS(s) + H2O

CH4 + CO2

2) Primary reforming (addition of water)

CH4 + H2O CO + 3H2
CnH2n+2 + nH2O nCO + (2n+1)H2
H>0 | T= 800 C | p= 30 atm | Catalyst: Ni | conversion (CH4) < 70%

3) Secondary reforming (addition of hot air)

CH4 + H2O CO + 3H2
1
CH4 + O2 CO + 2H2
2
CH4 + CO2 2CO + 2H2
2H2 + O2 2 H2O
T= 950 C | p= 30 atm| Cat: Ni
The combustion of the methane is exothermic (H<0) (produces heat) but the heat
produced is not enough to maintain the temperature at 950 C. Thus the
combustion of a part of the hydrogen (very exothermic (H<<0) must take place.
 H2 + CO + N2 + CO2
[H2O + O2 + CH4 + H2S] traces

4) Shift reaction
CO + H2O CO2 + H2
H<0 | Cat: CuO, ZnO, Al2O3

H2 + N2 + CO2
[H2O + CO (<0.5%) + O2 + CH4 + H2S] traces

5) Removal of CO2
Absorption of CO2 in solvents as methanol or organic
amines

H2 + N2
[H2O + CO (<0.5%) + O2 + CO2 + CH4 + H2S] traces

6) Removal of CO2 and H2O

CO2 and H2O are adsorbed on zeolites

7) Removal of CH4
Washing in columns with liquid nitrogen (p= 80 bar)
Methane and other hydrocarbons condense
 it's reached the optimal ratio of N2 and H2 (1:3) if the
process is used to produce the mixture of gases for the
production of ammonia

H2 + N2
[H2O + CO + O2 + CO2 + CH4 + H2S] traces

8) Methanation
CO + 3 H2 CH4 + H2O
CO2 +4 H2 CH4 + 2H2O
H<0 |p=30 atm | T= 250/300 C | Cat: Ni
The water produced in the reaction is removed for
adsorption on zeolites

H2 + N2
[H2O + CO (<10ppm) + O2 + CO2 + CH4(1%) + H2S] traces

9) Condensation of CH4 (optional)

To remove methane (and Argon) its used a condensation
at low temperatures